1. Field of the Invention
The present invention relates to a conductive rubber composition, and a manufacturing method and a conductive rubber member thereof. More particularly, it relates to a conductive rubber composition having a low hardness and a low distortion, and exhibiting a small range of variations in its volume specific resistance value and low dependence on environment, and a manufacturing method thereof. Further, it relates to a conductive rubber member obtained using this composition and used in image forming apparatuses such as electrophotographic apparatuses and electrostatic recording apparatuses.
The present invention provides wide application in rubber members used in auto parts, hoses, belts, various rolls for copiers, facsimiles, printers, and the like, footwear, AV devices, OA devices, sealants, and the like, especially, various rubber members used in printers by means of electrophotography, electrostatic recording, and the like.
2. Prior Art
In recent years, semi-conductive elastic rolls have received attention as transferring members, and contact charging members with respect to toners of dry electrophotographic apparatuses with advances in electrophotographic technology. Thus, they are used for developing rolls, transferring rolls, and the like. The semi-conductive members used for such applications are required not only to have prescribed electric resistance values, but also to exhibit a small range of positional variations in electric resistance and low dependence of the electric resistance on the applied voltage, and to vary less in electric resistance when continuously energized. They are further required to have a narrow range of variations in electric resistance values even for environmental changes ranging from low temperature and low humidity to high temperature and high humidity.
In general, conductivity (volume specific resistance value: 1xc3x97106 xcexa9xc2x7cm or less) is imparted by mixing of carbon black and the like. Accordingly, with a conventional method, the dosage thereof is increased, and hence the viscosity of the system is increased, thereby interfering with the processability and raising the hardness. Consequently, the contact area with a photosensitizing drum decreases, entailing a problem in printing properties. For preventing this, there is known a conductive rubber composition having a prescribed electric resistance and hardness, and suitable as a rubber material for electrically conductive blades used in image forming apparatuses such as electrophotographic copying machines and electrostatic recording apparatuses (Japanese Patent Laid-Open Publication No. Hei-10-87897). This composition contains a vulcanized product of a rubber component A (epoxy containing rubber, and the like.), a rubber component B (SBR, NBR, and the like.) vulcanized by a different mechanism from the case of the rubber component A, and conductive particles. The conductivity and hardness are adjusted in a prescribed range by increasing the concentration of the conductive particles in the rubber component B. However, a considerable portion of the conductive particles transfers toward the rubber component A during kneading. Accordingly, it is difficult to impart the desired conductivity with stability. Further, the composition requires two types of vulcanizing agents each having a different vulcanization mechanism. Thus, two-step vulcanization is required to be carried out, resulting in a complicated procedure. Further, in WO97/03122, there is disclosed a method for manufacturing a conductive rubber composition, which comprises: a step of kneading a rubber component (A), a rubber component (B) to be vulcanized by a different mechanism from the case of the rubber component (A), and the vulcanizing agent of the rubber component (A) to vulcanize only the rubber component (A), and a step of subsequently adding the vulcanizing agent of the rubber component (B), and conductive particles thereto. However, this method also entails insufficient dispersion of the conductive particles, resulting in variations in conductivity.
Further, when a plasticizer and a softening agent are added in large amounts to achieve lower hardness, insufficient dispersion of a conductivity imparting agent unacceptably occurs, resulting in variations in conductivity.
[Problems to be Solved by the Invention]
The present invention has been achieved in view of the foregoing. It is therefore an object of the present invention to provide a conductive rubber composition which not only shows a prescribed electric resistance value, but also varies less in electric resistance, and has a narrow range of variations in electrical resistance values even for environmental changes ranging from low temperature and low humidity to high temperature and high humidity, and is excellent in low hardness and low compression set. It is a further object of the present invention to provide a method for manufacturing such a conductive rubber composition, and a conductive rubber member obtained using this composition.
The present inventors have conducted a rigorous study, and consequently they have found that the objects of the present invention can be achieved by providing the following conductive rubber composition. That is, the composition contains a crosslinked particulate polymer (A1), an uncrosslinked polymer (A2, generally a linear polymer), and a conductivity imparting agent (B), and the aforesaid conductivity imparting agent (B) is unevenly distributed and the more conductivity imparting agent (B) exist in the uncrosslinked polymer (A2) than in the crosslinked particulate polymer (A1) by starting the kneading at such a temperature that the Moony viscosity of the uncrosslinked polymer is equal to or less than the Moony viscosity of the crosslinked particulate polymer. The present invention has been achieved based on this finding.
A conductive rubber composition, according to a first aspect of the present invention, is characterized by comprising: a crosslinked particulate polymer (A1), an uncrosslinked polymer (A2), and a conductivity imparting agent (B), wherein the aforesaid crosslinked particulate polymer (A1) is a nonpolar polymer, the aforesaid uncrosslinked polymer (A2) is a polar polymer, and the aforesaid conductivity imparting agent (B) is unevenly distributed and the more conductivity imparting agent (B) exist in the uncrosslinked polymer (A2) than in the crosslinked particulate polymer (A1).
A method for manufacturing a conductive rubber composition, according to a second aspect of the present invention, is characterized by comprising: a step of starting the kneading of the composition at such a temperature (Txc2x0 C.) wherein the following expression (1) holds, the aforesaid composition comprising a crosslinked particulate polymer (A1), an uncrosslinked polymer (A2), and a conductivity imparting agent (B), the crosslinked particulate polymer (A1) being a nonpolar polymer, and the uncrosslinked polymer (A2) being a polar polymer, where the temperature (Txc2x0 C.) denotes the temperature at which kneading is started, that is, it is not a temperature during kneading, but it virtually represents the set temperature of a kneading machine:
Moony viscosity (Txc2x0 C.) of the uncrosslinked polymer (A2)/Moony viscosity (Txc2x0 C.) of the crosslinked particulate polymer
xe2x80x83(A1)xe2x89xa61.0xe2x80x83xe2x80x83(1)
Each of these Moony viscosities is individually determined for the crosslinked particulate polymer and the uncrosslinked polymer at the fourth minute after preheating each polymer for 1 minute at a prescribed temperature, and then rotating it for 4 minutes at 2 rpm using a rotor.
A conductive rubber member, according to a third aspect of the present invention, is characterized by being obtained by vulcanizing the aforesaid conductive rubber composition and used in an image forming apparatus.
[Effect of the Invention]
According to the rubber composition of the present invention, there can be provided a conductive rubber member (rubber sheet, and the like.) which exhibits a small range of positional variations in electric resistance and a narrow range of variations in electric resistance values even for environmental changes ranging from low temperature and low humidity to high temperature and high humidity, and has a low hardness and a large breaking extension, i.e., offers excellent properties in all respects in a well-balanced manner. That is, the conductive rubber member of the present invention exhibits the aforementioned excellent properties.
Further, according to the manufacturing method of the present invention, a conductive rubber composition exhibiting the excellent properties described above can be manufactured easily even without changing the type of vulcanizing agent nor performing two-stage vulcanization.
Accordingly, the rubber composition and the like of the present invention are particularly preferred for use in fields where conductivity or antistatic properties are required, such as LCD-related fields, LSI-related fields, IC-related fields, OA devices, AV devices, and home appliances, especially, charging, developing, and transferring rolls and the like of printers, copiers, and the like, using electrophotographic technology.
The present invention will be described in detail below.
The xe2x80x9ccrosslinked particulate polymer (A1)xe2x80x9d in the present invention is a nonpolar polymer. Specific examples thereof include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-xcex1-olefin-nonconjugated diene rubbers such as ethylene-propylene-nonconjugated diene rubber, and ethylene-butene-nonconjugated diene rubber, and ethylene-vinyl acetate rubber. Among these rubbers, ethylene-propylene-nonconjugated diene rubber, butadiene rubber, and styrene-butadiene rubber are preferred. Styrene-butadiene rubber is more preferred. These rubbers may be used alone, or in blends of two or more thereof.
The crosslinked particulate polymer may has a toluene insoluble matter content of 80% by weight or more, and the content is preferably 90% by weight or more, and more preferably 92% by weight or more.
As monomers constituting the crosslinked particulate polymers, or monomers used for manufacturing thereof, {circle around (1)} aliphatic conjugated diene monomers and/or olefin monomers (below, referred to as xe2x80x9cmonomers {circle around (1)}xe2x80x9d) are essential. As the crosslinked particulate polymers, crosslinked particulate polymers obtained by copolymerizing crosslinkable monomers (below, referred to as xe2x80x9cmonomers {circle around (2)}xe2x80x9d) are preferred. Further, as this crosslinked particulate polymer, except the method of this copolymerization, for example, the product gained by smashing vulcanizing rubber into powders after production of it, or the product A1+A2) gained by vulcanizing only the above polymer dynamically by mixing the polymer that can be vulcanized dynamically (A1xe2x80x2), the polymer not to be vulcanized dynamically (an uncrosslinked polymer, A2) and a vulcanizing agent are quoted.
Examples of the aliphatic conjugated diene monomers of the aforementioned monomers {circle around (1)} include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Further, examples of the aforementioned olefin monomers include ethylene, propylene, butene, styrene, xcex1-methylstyrene, and vinyltoluene. These monomers can be used alone or in mixtures of two or more thereof. In the repeating unit in the particulate copolymer, the content of the monomer {circle around (1)} unit is in the range of 10 to 95 mol %, and preferably in the range of 30 to 90 mol %. When the content of the monomer {circle around (1)} unit is less than 10 mol %, the resulting conductive rubber composition has insufficient mechanical properties. On the other hand, when it exceeds 95 mol %, the resulting conductive composition has an insufficient conductivity. Thus, both the cases are undesirable.
Examples of the nonconjugated diene monomers used for the ethylene-xcex1-olefin-nonconjugated diene rubbers include cyclopentadiene, dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methyl-2-norbornene,5-isopropenyl-2-norbornene, 5-(1-butenyl)2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9-tetrahydroindene, 2,2xe2x80x2-dicyclopentenyl, trans-1,2-divinylcyclobutane, 2-methyl-1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,4-hexadiene, 1,8-nonadiene, 1,9-decadiene, 3,4,7-octatriene, 5-methyl-1,8-nonadiene, dicyclooctadiene, methylenenorbornene, and 5-ethylidene-2-norbornene and the like. These may be used alone, or in mixtures of two or more thereof.
Examples of the aforementioned monomer {circle around (2)} include ethylene glycol di(meth)acrylate, propylene glycol-di(meth)acrylate, 1,4-butanediol-di(meth)acrylate, 1,6-hexanediol-di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane-tri(meth)acrylate, pentaerithritol-tri(meth)acrylate, pentaerithritol-tetra(meth)acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, and hexamethylene-di(meth)acrylate. These monomers {circle around (2)} can be used alone, or in mixtures of two or more thereof.
In the repeating unit in the particulate copolymer, the content of the monomer {circle around (2)} unit is in the range of 0.1 to 20 mol %, and preferably in the range of 0.5 to 10 mol %. When the content of the monomer {circle around (2)} unit is less than 0.1 mol %, the resulting conductive rubber composition has an insufficient conductivity. On the other hand, when it exceeds 20 mol %, the resulting conductive rubber composition has insufficient mechanical properties. Thus, both cases are undesirable.
The aforementioned crosslinked particulate polymer can be manufactured by an emulsion polymerization method or a suspension polymerization method using a radical initiator. However, the emulsion polymerization method is preferred in small sizes of the particle size and uniformity of the particle size. Examples of the radical initiator include (1) organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl hydropeoxide, cumene hydroperoxide, para-menthane hydroperoxide, di-t-butyl peroxide, and dicumyl peroxide; (2) diazo compounds typically including azoisobutyronitrile; (3) inorganic peroxides typically including potassium persulfate; and (4) redox system catalysts typically including combinations of these peroxides and ferrous sulfate. These radical initiators can be used alone, or in mixtures of two or more thereof.
Examples of the emulsifying agent used for emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may also be fluorine-based surfactants. These emulsifying agents can be used alone, or in mixtures of two or more thereof.
Examples of the suspension stabilizer used for suspension polymerization include polyvinyl alcohol, sodium polyacrylate, and hydroxyethyl cellulose. These suspension stabilizers can be used alone, or in combination of two or more thereof. In emulsion polymerization or suspension polymerization, polymerization drugs such as each monomer and radical initiator may be added in total amounts at the time of starting the reaction.
Although the polymerization is generally carried out at 0 to 80xc2x0 C. in a reactor where oxygen has been removed, the operation conditions such as temperature and stirring can also be changed appropriately during the reaction. The polymerization can be accomplished by either a continuous process or a batch process.
The average particle diameter of the crosslinked particulate polymer (A1) may be 25 xcexcm or less, preferably 10 xcexcm or less, and more preferably 5 xcexcm or less. When it exceeds 25 xcexcm, variations undesirably occur in the volume specific resistance value of the resulting conductive rubber composition.
The hardness of the crosslinked particulate polymer (A1) is preferably in the range of 45 to 80 in duro A. When it is 45 or less, the degree of uneven distribution of the conductivity imparting agent (B) in the uncrosslinked polymer (A2) is reduced. Accordingly, the conductivity imparting agent (B) must be undesirably increased in an amount for providing the desired conductivity, resulting in an increase in hardness. On the other hand, when it exceeds 80, the resulting conductive rubber composition undesirably has insufficient mechanical properties.
The uncrosslinked polymer (A2) in the present invention is a polar polymer, and generally linear polymer. Specific examples thereof include chloroprene rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, polysulfide rubber, epichlorohydrin rubber, epichloroethylene oxide rubber, urethane rubber, silicone rubber, and fluororubber. Among these rubbers, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, acrylic rubber, ethylene-acrylic rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, urethane rubber, epichlorohydrin rubber, and epichlorohydrin-ethylene oxide rubber are preferred. Acrylic rubber or acrylonitrile-butadiene rubber is preferable. These rubbers may be used alone, or in blends of two or more thereof.
The blending ratio (weight ratio)of the crosslinked particulate polymer (A1) to the uncrosslinked polymer (A2) is 10/90 to 90/10, preferably 20/80 to 80/20, and more preferably 25/75 to 75/25. When the ratio of the crosslinked particulate polymer (A1) is less than 10, the conductivity imparting agent (B) is undesirably required to be added in a large amount in order to obtain the desired volume specific resistance value. On the other hand, when it exceeds 90, the mechanical properties undesirably become insufficient.
Further, a difference in the solubility parameter between said uncrosslinked polymer (A2) and the crosslinked particulate polymer (A1) may be not less than 0.5, the difference is preferably not less than 0.6, and more preferably not less than 0.7, and generally not more than 5. Further, the difference is generally 0.7-3.0, and preferably 0.7-2.5.
The conductivity imparting agent (B) in the present invention reduces the electric resistance of the polymers by being dispersed in the polymers. In general, it takes the form of a particle.
Specific examples of the conductivity imparting agent (B) include (1) carbon blacks such as EC (Extra Conductive), ECF (Extra Conductive Furnace), SCF (Super Conductive Furnace), CF (Conductive Furnace), and acetylene black (including Ketjen black EC (EC600JD)), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), HAF (High Abrasion Furnace), FEF (Fast Extruding Furnace), GPF (General Purpose Furnace), SAF (Semi-Reinforcing Furnace), FT (Fine Furnace), and MT (Medium Thermal); (2) metal oxides such as ZnO (Al doped), SnO2 (antimony oxide doped), TiO2, SnO2 (antimony oxide doped), metal-coated SnO2, metal-coated TiO2, K20-nTiO2/SnO2 (antimony oxide doped), SnO2 (antimony oxide doped), and metal-coated composite oxide; (3) metal single bodies such as copper powder, silver powder, and aluminium powder; and (4) conductive polymers such as polyaniline, polypyrrole, and polyacetylene. Among them, carbon blacks are preferred.
The primary particle diameter of the conductivity imparting agent (B), especially of the carbon black is in the range of 10 to 100 nm, preferably 20 to 80 nm, and more preferably 30 to 60 nm. The amount of the conductivity imparting agent (B) to be added is preferably in the range of 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 2 to 40 parts by weight. When it is less than 0.5 parts by weight, an error in measurement in weighing at the time of addition presents a problem. On the other hand, when it exceeds 100 parts by weight, the low hardness and low compression set characteristics are undesirably impaired.
The conductive rubber composition of the present invention is manufactured, for example, by the following methods:
(1) a method in which a crosslinked particulate polymer, an uncrosslinked polymer, and a conductivity imparting agent are kneaded by means of a kneading machine;
(2) a method in which a water dispersion or an emulsion of an uncrosslinked polymer, and a water dispersion or an emulsion of a crosslinked particulate polymer are mixed, followed by solidifying and drying, and then a conductivity imparting substance is kneaded therein by means of a kneading machine; or
(3) a method in which an uncrosslinked polymer and a conductivity imparting agent are previously kneaded by means of a kneading machine, and then a crosslinked particulate polymer is added and kneaded therein.
Examples of a kneading machine include closed kneading machines (for example, Banbury mixer, internal mixer, and kneader), and open rolls. As the kneading conditions, the kneading starting temperature (the set temperature of a kneading machine) is such a temperature that the above-described expression holds between the Moony viscosities of the crosslinked particulate polymer (A1) and the uncrosslinked polymer (A2). If it falls outside the condition, the degree of uneven distribution of the conductivity imparting agent (B) in the uncrosslinked polymer in the resulting conductive rubber composition becomes insufficient. As a result, undesirably, the volume specific resistance value does not reach the desired level sufficiently, and further, variations increase with each manufacturing. In addition, variations undesirably increase in mechanical properties.
For example, when the crosslinked particulate polymer (A1) is styrene-butadiene series rubber, and the uncrosslinked polymer (A2) is acrylonitrile-butadiene series rubber, the kneading starting temperature can be 80xc2x0 C. or more (preferably 90xc2x0 C. or more, generally 150xc2x0 C. or less).
In the conductive rubber composition of the present invention, if required, ionic conductivity imparting agents, vulcanizing agents, fillers, colorants, lubricants, metal oxides, softening agents, plasticizers, aging inhibitors, processing aids, scorch retarders, pulling agents, oxidation inhibitors, activators, ultraviolet absorbers, tackifiers, dehydrating agents, waxes, light stabilizers, internal mold lubricants, foaming agents, foaming aids, antibacterial agents, flame retardants, peptizing agents, and the like can be added.
Examples of the ionic conductivity imparting agent include salts of the group I metals of the Periodic Table such as LiCF3SO3, NaClO4, LiClO4, LiAsF6, LiBF4, NaSCN, KSCN, and NaCl; ammonium salts such as NH4Cl, NH4SO4, NH4NO3, and quaternary ammonium salts of perchloric acid; salts of the group II metals of the Periodic Table such as Ca(ClO4)2,and Ba(ClO4)2; complexes of these salts and polyhydric alcohols such as 1,4-butane diol, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol or derivatives thereof; complexes of these salts and monools such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, polyethylene glycol monomethyl ether, and polyethylene glycol monoethyl ether; cationic surfactants such as quaternary ammonium salts; anionic surfactants such as aliphatic sulfonates, alkylsulfuric acid ester salts, and alkylphosphoric acid ester salts; nonionic surfactants such as polyethylene glycol adducts of higher alcohols and fatty acid diesters of polyalkylene glycol; and amphoteric surfactants such as betaine.
The above-described quaternary ammonium salts of perchloric acid are represented, for example, by the following general formula (I). The above-described aliphatic carboxylic acid diesters of polyalkylene glycol are represented, for example, by the following general formula (II). Examples thereof include at least one compound selected from the group consisting of the quaternary ammonium salts of perchloric acid and/or aliphatic carboxylic acid diesters of polyalkylene glycol.
[R4xe2x80x94Oxe2x80x94(A1xe2x80x94O)mxe2x80x94C(O)]xxe2x80x94R1xe2x80x94[C(O)xe2x80x94(Oxe2x80x94A2)nxe2x80x94N+(R2)(R3)(R5).ClO4xe2x88x92]yxe2x80x83xe2x80x83(I)
(where R1 denotes a group other than all the carboxyl groups of an aliphatic or aromatic carboxylic acid of 2 to 20 carbon atoms; R2 and R3 each individually denote an alkyl group of 1 to 20 carbon atoms or a hydroxyalkyl group of 1 to 20 carbon atoms; A1 and A2 each individually denote an alkylene group of 2 to 4 carbon atoms; m is an integer of 0 to 20; n is an integer of 1 to 20; R4 denotes an alkyl group of 4 to 22 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or Rxe2x80x2 CONHRxe2x80x3 (where Rxe2x80x2 is an alkyl group of 1 to 20 carbon atoms or an alkenyl group of 1 to 20 carbon atoms, and Rxe2x80x3 is an alkylene group of 1 to 10 carbon atoms.); R5 denotes an alkyl group of 1 to 20 carbon atoms; x is an integer of 0 to 3; y is an integer of 1 to 4; and (x+y) equals the valence of R1.)
R6xe2x80x94C(O)xe2x80x94Oxe2x80x94(R7xe2x80x94O)kxe2x80x94C(O)xe2x80x94R8xe2x80x83xe2x80x83(II)
(where R6 and R8 each individually denote a group other than the carboxyl groups of an aliphatic monocarboxylic acid of 4 to 18 carbon atoms; R7denotes an alkylene group of 2 to 4 carbon atoms; and k is an integer of 2 to 30.)
Different vulcanizing agents can be used depending upon the rubber species used. Examples thereof include sulfur containing vulcanizing agents, organic peroxides, quinoid vulcanizing agents, resin vulcanizing agents, metal oxide vulcanizing agents, sulfur containing organic compounds, amine vulcanizing agents, triazine containing vulcanizing agents, polyol vulcanizing agents, metal soap containing vulcanizing agents, and maleimide containing vulcanizing agents.
Examples of the sulfur containing vulcanizing agents include powder sulfur, flowers of sulfur, high-dispersion sulfur, insoluble sulfur, precipitated sulfur, surface-treated sulfur, colloid sulfur, sulfur chloride, sulfur monochloride, and sulfur dichloride. When the sulfur containing vulcanizing agent is used, a vulcanization accelerator can be used.
Specific examples of the vulcanization accelerator include (1) aldehyde ammonias such as hexamethylenetetramine and acetaldehyde-ammonia; (2) aldehyde amines such as n-butyl aldehyde-aniline condensation product, butyl aldehyde-monobutylamine condensation product, heptaldehyde-aniline reaction product, and tricrotonylidene tetramine; (3) guanidine salts such as diphenylguanidine, di-o-tolylguanidine, ortho tolyl biguanide, and diortho tolyl guanidine salts of dicatechol borate; (4) imidazolines such as 2-mercaptoimidazoline; (5) thiazoles such as 2-mercaptobenzothiazole, 2-mercaptothiazoline, dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenylthio)benzothiazole, 2-(N,N-diethylthio carbamoylthio)benzothiazole, 2-(4xe2x80x2-morpholino dithio)benzothiazole, and 4-morphonyl-2-benzothiazyl disulfide; (6) sulfeneamides such as N-cyclohexyl-2-benzothiazyl sulfeneamide, N,N-dicyclohexyl-2-benzothiazyl sulfeneamide, N-oxydiethylene-2-benzothiazyl sulfeneamide, N,N-diisoprpyl-2-benzothiazyl sulfeneamide, and N-tert-butyl-2-benzothiazyl sulfeneamide; (7) thioureas such as thiocarbamide, ethylene thiourea(2-mercaptoimidazoline), diethyl thiourea, dibutyl thiorurea, mixed alykyl thiourea, trimethyl thiourea, and dilauryl thiourea; (8) dithiocarbamates such as sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butylcarbamate, lead dimethyldithiocarbamate, lead diamyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diamyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cadmium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, bismuth dimethyldithiocarbamate, piperidine dimethyldithiocarbamate, pipecoline methylpentamethylenedithiocarbamate, and activated dithiocarbamate; (9) thiurams such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, activated tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, and mixed alkyl thiuram disulfide; (10) xanthates such as sodium isopropyl xanthogenate, zinc isopropyl xanthogenate, and zinc butyl xanthogenate; and (11) 4,4xe2x80x2-dithiomorpholine, aminodialkyl dithiophosphate, zinc-o, o-n-butyl phosphorodithioate, 3-mercaptoimidazoline-thione-2, and thioglycolic acid ester. These can be used alone, or in mixtures of two or more thereof.
Examples of the organic peroxides include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, di-tert-butyl peroxide, tert-butylcumyl peroxide, di-cumyl peroxide, 2,5-di-methyl-2,5-di(tert-butylperoxy)hexane, 2,5-di-methyl-2,5-di(tert-butylperoxy)hexyne, 1,3-bis(tert-butylperoxy-isopropyl)benzene, tert-butylperoxy-isopropyl carbonate, acetylcyclohexylsulfonyl peroxide, isobutyl peroxide, di-isopropylperoxy dicarbonate, di-allylperoxy dicarbonate, di-n-propylperoxy dicarbonate, di-(2-ethoxyethyl)peroxy dicarbonate, di(methoxyisopropyl)peroxy dicarbonate, di(2-ethylhexyl)peroxy dicarbonate, tert-hexylperoxy neohexanate, di(3-methyl-3-methyloxybutyl)peroxy dicarbonate, tert-butylperoxy neodecanate, tert-hexylperoxy neodecanate, tert-butylperoxy neohexanate, 2,4-dichlorobenzoyl peroxide, tert-hexylperoxy pivalate, tert-butylperoxypivalate, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumylperoxy octate, acetyl peroxide, tert-butylperoxy(2-ethylhexanate), benzoyl peroxide, tert-butylperoxy isoisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxymaleic acid, tert-butylperoxy laurate, tert-butylperoxy 3,3,5-trimethylhexanate, cyclohexanone peroxide, tert-butylperoxy allyl carbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,2,-bis(tert-butylperoxy)octane, tert-butylperoxy acetate, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxy benzoate, n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butyldiperoxy isophthalate, methyl ethyl ketone peroxide, xcex1, xcex1xe2x80x2-bis(tert-butylperoxy-m-isopropyl)hexane, di-isopropylbenzene-hydroperoxide, p-methane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5,-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide. These can be used alone, or in mixtures of two or more thereof.
When an organic peroxide is used as a vulcanizing agent, a co-crosslinking agent can be added in combination with the organic peroxide. Examples of the co-crosslinking agent include p-quinonedioxime, p-benzoquinonedioxime, p,pxe2x80x2-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, N-methyl-Nxe2x80x2-4-dinitrosoaniline, N,Nxe2x80x2-m-phenylenedimaleimide, dipentamethylenethiuram pentasulfide, dinitrosobenzene, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, triazine thiol, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane triacrylate, erithritol tetramethacrylate, trimethylolpropane trimethacrylate, diallyl melamine, trimethacrylate, dimethacrylate, divinyl adipate, vinyl butyrate, vinyl stearate, liquid polybutadiene rubber, liquid polyisoprene rubber, liquid styrene-butadiene rubber, liquid acrylonitrile-butadiene rubber, magnesium diacrylate, calcium diacrylate, aluminium acrylate, zinc acrylate, stannous acrylate, zinc methacrylate, magnesium methacrylate, and zinc dimethacrylate.
Examples of the resin vulcanizing agent include alkylphenol-formaldehyde resin, melamine-formaldehyde condensation product, triazine-formaldehyde condensation product, octylphenol-formaldehyde resin, alkylphenol sulfide resin, and hexamethoxymethyl melamine resin.
Examples of the metal oxide vulcanizing agent include zinc oxide, magnesium oxide, and lead monoxide.
Examples of the sulfur containing organic vulcanizing agents include morpholine disulfide, alkylphenol disulfide, N,N-[dithio-bis(hexahydro-2H-azepinone-2), thiuram polysulfide, and 2-(4-[morpholinodithio]benzothiazole.
Examples of the polyamine containing vulcanizing agents include hexamethylenediamine carbamate, N,Nxe2x80x2-1,6-hexanediamine, hexamethylenediamine, triethylene tetramine, tetraethylene pentamine, 4,4xe2x80x2-methylenebis(cyclohexylamine)carbamate, N,Nxe2x80x2-dicynnamylidene-1,6-hexadiamine, and ammonium benzoate.
Examples of the triazine containing vulcanizing agents include 2,4,6-trimercapto-S-triazine, and 2-di-n-butylamino-4,6-dimercapto-s-triazine.
Examples of the polyol containing vulcanizing agents include bisphenol A, bisphenol AF, hydroquinone, and pentaerithritol.
Examples of the metal soap containing vulcanizing agents include sodium stearate, potassium stearate, sodium oleate, and potassium oleate.
Examples of the maleimide containing vulcanizing agents include N,Nxe2x80x2-m-phenylenedimaleimide.
Examples of the filler include ground calcium carbonate, chalk, light calcium carbonate, microfine activated calcium carbonate, special calcium, basic magnesium carbonate, kaolin clay, calcined clay, pyrophylite clay, silan-finished clay, natural silicic acid, synthetic silicic anhydride, synthetic hydrous silicic acid, synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminium silicate, magnesium carbonate, aluminium hydroxide, magnesium hydroxide, magnesium oxide, kaolin, sericite, talk, powder talk, wallastonite, zeolite, xonotlite, mica, asbestos, PMF (Processed Mineral Fiber), sepiolite, potassium titanate, elestadite, gypsum fiber, glass balloon, silica balloon, hydrotalcite, fly ash balloon, shirasu balloon, carbonaceous balloon, organic balloons such as phenol resin, urea resin, styrene resin, and saran resin, alumina, barium sulfate, aluminium sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roving, milled glass fiber, and glass flake), cut fiber, rock fiber, micro fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, reclaimed rubber, rubber powder, ebonite powder, shellac, and wood flour.
Examples of the colorant include (1) inorganic pigments such as titanium oxide, zinc oxide, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, carbon black, white lead, and red iron oxide; and (2) organic pigments such as insoluble disazo type, condensation azo type, isoindolinone type, benzimidazolone type and aniline black.
Examples of the lubricant include stearic acid, oleic acid, lauric acid, dibutylammonium oleate, zinc stearate, calcium stearate, potassium stearate, and sodium stearate.
Examples of the metal oxide include zinc white, active zinc white, surface-treated zinc white, zinc carbonate, composite zinc white, composite active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, microfine calcium hydroxide, lead monoxide, red lead, and white lead.
The following typical method is performed as the method of low hardening of the conductive composition of the present invention. The method adding a softening agent and a plasticizer and/or the method making sponge rubber adding a foaming agent and foaming assistant agent is is effective. In the above there are a lot of problems, because the variation of electrical resistance of a solid rubber is apt to be amplified further by changing solid rubber to sponge rubber. However, according to the conductive rubber composition of the present invention, the variation of electrical resistance of solid rubber is so very small that the dispersion of electrical resistance of a sponge rubber is also small. Examples of the foaming agent include an inorganic foaming agent such as ammonium carbonate, sodium bicarbonate and sodium nitrate anhydride and the like; and an organic foaming agent such as dinitorosopentametylenetetraminn, N,Nxe2x80x2-dimetyl-N,Nxe2x80x2dinitrosoterephthalamide,benzenesurufonylhydrazid, p,pxe2x80x2-oxybis(benzenesufonyl hydrazide), 3,3xe2x80x2-disurfonehydrazidediphenyl sulufone, azobisobutyronitrile, azobisformamide. These may be used alone, or in mixtures of two or more thereof. Further, it is also possible to use the foaming aids such as azo-system, organic acid-system, metal salt-system and the like with the above-mentioned foaming agent.
Examples of the softening agent include petroleum softening agents, vegetable oil softening agents, and factices. Examples of the petroleum softening agents include aromatic type, naphthenic type, and paraffinic type softening agents. Examples of the vegetable oil softening agents include castor oil, cotton-seed oil, linseed oil, rape seed oil, soybean oil, palm oil, copra oil, arachis oil, and Japan wax. Examples of the factices include black factice, white factice, and semitransparent factice. Out of these, since a development roll is required to have no reactivity with a toner (to be excellent in elimination from a toner), the paraffinic and naphthenic types are particularly preferred in this regard.
Examples of the plasticizer include phthalic acid type, isophthalic acid type, tetrahydrophthalic acid type, adipic acid type, azelaic acid type, sebacic acid type, dodecane-2-acid type, maleic acid type, fumaric acid type, trimellitic acid type, citric acid type, itaconic acid type, ricinolic acid type, stearic acid type, polyether type, polyester type, polyether ester type, phosphate type, glycol type, and epoxy type plasticizers. Among them, sebacic acid type is preferred in terms of elimination from a toner.
Examples of the aging inhibitor include naphthylamine type, diphenylamine type, p-phenylenediamine type, quinoline type, hydroquinone derivative type, mono-, bis-, tris-, poly-phenol type, thiobisphenol type, hindered phenol type, phosphite type, imidazole type, nickel dithiocarbamate type, and phosphoric acid type aging inhibitors.
The conductive rubber composition obtained by the above-described method is then vulcanized to manufacture a conductive rubber member. In this process, in order to vulcanize (crosslink) the conductive rubber composition, a vulcanizing agent (crosslinking agent) is added by a kneading machine, followed by crosslinking forming. As this vulcanizing agent, the ones described above can be used. Further, when the kneading temperature is low, or when the vulcanizing agent fails to react during kneading as in the case of a vulcanizing agent requiring a high reaction temperature, it is also possible that the vulcanizing agent be previously added from the beginning and not added during kneading.
The composition is molded into the desired form to be adaptable for use as the conductive rubber members of rolls, blades, belts, and the like. There is no particular restriction on the molding method, and conventional methods can be adopted. Examples thereof include press molding, transfer molding, extrusion, and injection molding. Further, the molded products can also be subjected to crosslinking by electron beam, high-frequency wave, air heating, or the like.
The range of variations (a difference between the maximum value and the minimum value) in volume specific resistance value among the same batches is 1.0 xcexa9xc2x7cm or less, preferably 0.5 xcexa9xc2x7cm or less, and more preferably 0.4 xcexa9xc2x7cm or less, under the measurement conditions shown in the following examples. Further, as for the environment dependence determined under the measurement conditions shown in the following examples, a difference between the volume specific resistance value (L/L value) at 10xc2x0 C. under 15% RH, and the volume specific resistance value (H/H value) at 30xc2x0 C. under 85% RH is 0.7 xcfx89xc2x7cm or less, preferably 0.5 xcexa9xc2x7cm or less, and more preferably 0.4 xcexa9xc2x7cm or less.
Below, the rubber composition, according to the present invention, will be described by way of examples, which should not be construed as limiting the scope of the present invention.